Sulfonamide substituted p-phenylenediamines containing o-alkoxy groups as silver halide photographic developers



Patented Apr. 10, 1951 UNITED STATES PATENT OFFICE Arnold Weissberger,Dudley B. Glass, and Paul W. Vittum, Rochester, N. Y., assignors toEastman tion of New Jersey N Drawing.

This invention relates to photographic developers and more particularlyto photographicdevelopers of the substituted p-phenylenediamine yp Thisapplication isa. continuation-in-part of application Serial No..654,528, filed March 14, 1946, now abandoned.

It is known that p-phenylenediamine photographic developers are valuablecompounds for producing fine grain black-and-white photographic images,and also, that these compounds, especially when they contain alkylsubstituents, are useful as developers in processes for producingcolored photographic images. The phenylenediamine developers, however,have several defects. A common 'difiiculty encountered when using thesedevelopers i their low activity and the low contrast and emulsion speedobtained with them. Other disadvantages are their low solubility indeveloping solutions and their allergenic character, that is, theirpoisonousness to the human skin. These latter defects have been solved,according to Weissberger U. S. Patent 2,193,015, by adding a sulfonamidegroup to one of the nitrogen atoms of p-phenylenediamine. Developers ofthis type, however, exhibit low developing activity.

A principal object of the present invention is, therefore, to providenew developing agents of the substituted p-phenylenediamine type havinghigh developing activity and which are capable of giving high contrastand emulsion speed.

We have discovered that the rate of development with sulfonamidesubstituted p-phenylenediamines is remarkably increased by substitutingan alkoxy group in the benzene ring in ortho position with respect tothe primary amino group. These novel compounds have the followinggeneral formula:

HaN N Kodak Company, Rochester, N. Y., a corpora- Application February27, 1947, 'Serial No. 731,420

11 Claims.

Specific compounds which we contemplate.

using include: 1 CiHt HiN N\ (CH2)2NHS OgCHa CgHs4-amino-SethoXy-N-ethyI-N(fi-inethylsulfonamidoethyl) aniline4-amino-N-methyl-N-(fi-methylsulfonamidoethyl)-mis dine4-amino-N-ethy1-N- (B-methylsultonamidoethyl) -m-anisidine4-amino-3-prop oxy-N-propyl-N- (fimethylsulfonamidoethyl) aniline 5 I vI CH3 (CHZMNHS OgCHa CH3 4-amin0-3-methoxy-5-methyl-N -etl1yl-N(B-methylsultonamidoethy1)-aniline 4-amino-3,5-diethoxy-N-(B-methylsulfonamidoethyl) aniline The preparation of these compounds isillus-.

trated by the preparation of 4-amino-3-ethoxy- N ethyl N r (Emethylsu1fonamidoethyl).-

3 aniline, which may be synthesized by the following methods:

(a) N02 ND: NE:

C2H5I H:

catalyst OH OO:H OOzHs l 02H: I

NHC H:

or alternately: V O C2115 (b) COCHa..1

l nnoant NCzHs (CzHshSO (CH3CO)2O K hydrolyze OH OH BI'(CH9)2NH2.HBI

CHaCHiNHSQzCHs CH CH2NH3O2CH CHaCHaNHz NCzHa NC2H5 CzH HONO CHzSOzCl OCgHs O CzHs O CgHs H: catalyst CHzCHzN-HSOzCHg NCzHfl 002m; 1 I zy Thepreparation of 4-amino-N-ethyl-N-( 3- methylsulfonamido-ethyl)-m-phenetidine (Compound 1) may be illustrated-by the followinprocedure:

N-ethyl-m+acetophenetida-A mixture of one mole of m-phenetidine and onemole of ethyl iodide was warmed in a waterbath to 40 at whichtemperature an exothermicreaction began. The temperature was allowed toristo 60 and then was maintained atthis temperature for one hour firstby cooling and as the exothermic reaction subsided by Warming. Afterstanding overnight, the reaction mixture was stirred with 200 m1. ofwater and 100 ml. of 40% caustic until all of the solid had gone intosolution. The amines were extracted with ether, the ethereal solutionwas dried over solid sodium hydroxide and the ether was evaporatedx-Theresidue was added to 100 g. of acetic anhydr'id'with stirring andcooling so that the temperature did not rise above 50. This mixture washeated on the steam bath for thirty minutes, cooled and then stirredwith 150 ml. of water until all of the excess anhydride had decomposed.The mixture was made alkaline with 40% caustic solution and the productwas extracted with ether. The ethereal solution was dried oversolidsodium sulfate and the ether was evaporated. The residue was distilledunder reduced pressurecollecting the portion that boiled 4 at 105-110/1mm. as the desired product. The yield was 80 per cent.

N-ethyl-m-phenetidine.-One mole of N-ethylm-acetophenetide was boiledwith 150 ml. of water and 150 ml. of concentrated hydrochloric acid forsix hours. The reaction mixture was cooled, made alkaline with 200 m1.of 40% caustic solution and the amine was extracted with ether. Theethereal solution was dried over solid sodium hydroxide and the etherwas evaporated. The residue was distilled under reduced pressurecollecting the portion that boiled at l48-150/l7 as the desired product.The yield amounted to 90 per cent.

N-(fi aminoethyl) -N-ethyl-m phenetidine. A mixture of 1 mole ofN-ethyl-m-phenetidine and 0.5 mole of p-bromoethylamine hydrobromide wasstirred and heated at 140-150" for two and one-half hours. At the end ofthis time the reaction mixture was cooled and 225 ml. of water and ml.of 40% caustic solution were added. After all of the organic salts haddissolved, the product was extracted with ether. The ethereal solutionwas dried over solid sodium hydroxide and the ether was evaporated. Theresidu was distilled under reduced pressure collecting the portion thatboiled at 157-160/6 mm. as the desired product. The yield was per cent.

N ethyl N-(p methylsuljonamzdoethyl)emphenetidina-A mixture of 0.625mole of N-(flaminoethyl) -N-ethyl-m-phenetidine and 250 ml. of water wasstirred vigorously, and 80 g. (0.7 mole) of methane-sulfonyl chloridewas added during a period of 30 minutes, the temperature of the reactionmixture being kept at 15:5" during the addition of the chloride. Aftereach quarter of the acid chloride had been admitted, onefourth of asolution of 28 g. (0.7 mole) of sodium hydroxide in '75 ml. of water'wasintroduced. The mixture was then stirredfor two hours at 20-25 and madealkaline with ammonium hyadroxide. The amide was extracted withchloroxform, the chloroform solution was washed'with water and driedover sodium sulfate. The chloroform was evaporated under reducedpressure. The residue of crude amide amounted to per cent.

N -ethyl N (,8-metitylsuljonamidoethyl) -4,-nitroso-m-phenetz'dine.0nehalf mole of N-ethyl- N-(p methylsulfonamidoethyl) -m. phenetidine wasdissolved in a mixture of ml. of concentrated hydrochloric acid and 500ml. of hot water. This solution was cooled quicklyto 5 and. maintainedat this temperatureiwhile', a solutionof 39. g. (0.56 mole) of sodiumnitrite in 50ml. of water was added, withstirring, during a periodof"20f minutes. After standing" at 5? for one hourgthe" reaction mixturewas made alkalinelwith. ammo--. nium hydroxide. The precipitate,wa'sfiltered with suctionand washed With'jwater. I The moist produce.was' recrystallized twice from 500 m l. por tions of "Sf-A' alcohol anddried in air. The yield was85pe'rce'ntl' l -amino Nethyl-N-(p-methylsulfonamido ethyl) -m-phenetidine omalata one-half moleof N ethyl N (,B-methylsulfonamidoethyl) -4-nitroso-m-phenetidine wasdissolved" in 500 ml. of absolute alcohol and reduced in the presence ofRaney nickel at a hydrogen pressure of 4=5 lbs./in, anda temperatureof60. After the reduction was complete, the catalyst was filtered offand 0.5-' mole of powdered, anhydrous oxalic acid was added. The mixturewas warmed until all or the oxalic acid had dissolved and then, wascooled to;

1 0 and allowed to stand until crystallization was" complete. Thecrystals were filtered ofi, washed with absolute alcohol and dried inavacuum desiccator over sulfuric acid. The yield was 80 per cent.4-.-amino-N-ethyl-N-(,B-methylsulfonamidoethy1).-m'-anisidine (Compound3), 4-amino-3,5-diethoxy N-ethyl-N-(B-methylsulfonamidoethyl) aniline(Compound 6) and 4-amino-3-methoxyfi-methyl-N-ethyl-N(fi-methylsulfonamidoethyl)-aniline (Compound 5) can be prepared by thisprocedure from m-anisidine, 3,5.-diethoxyaniline and3-methoxy-5-methylaniline respectively.

. 4 amino N -,methyl N (,8 methylsulfonamidoethyD-m-anisidine(Compound-'2) can be prepared from meanisidine and 4 amino 3 propoxy Npropyl N (B methylsulfonamidoethyl) aniline (Compound 4) from 3-propoxyaniline by this procedure if instead of using ethyl iodide-inthefirst. step of the syntheses, methyl iodide is used for the firstcompound and propyl iodide'is used for the second.

The introduction of more 'than, one ethoxy group in the ortho positionswith respect to the primaryamino group as well as the introduction of analkyl group in one ortho position and. an alkoxy group in the othermustbe considered part of the present invention. Instead of ethoxygroups, other alkoxy groups may be used, including alkoxy groups withadditional substituents in the aliphatic radical, such as OH, Cl, OR,etc.

When used for the formation of colored photographic images, thedevelopers of our invention may be used in conjunctionwith any wellknown coupler compounds such as those described in Fischer U. S. Patent1,102,028, June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602,February 15, 1938; Mannes, Godowsky and Peterson U. S. Patent 2,115,934,April 26, 1938; and Mannes, Godowsky and Peterson U. S. Patent2,126,337, August 9, 1938.

The following examples, which are illustrative only, indicate developingsolutions which may be used according to our invention.

Example 1 A 4-amino-3 -ethoxy-N-ethy1-N- (ft-methylsulfonamidoethyl)-aniline grams 1 Sodium sulfite do 0.5 Sodium carbonate do 20 Water tocubic centimeters 1000 Coupler grams 1 Acetone cubic centimeters 50 AddB to A Example 2 For the formation of a fine grain black-andwhite image,the following developing solution may be used:

4-amino-N-ethyl-N- (p-methylsulfonamidoethyl) -m-anisidine grams 5Sodium sulfite do 30 Sodium carbonate do 30 Water to cubic centimeters1000 While we have given numerous examples of compounds illustrating ourinvention, it is obvious that various modifications can be made withoutdeparting from the spirit thereof. The specific alkoxy and alkylsubstituents may be varied and different combinations of thesesubstituents may be employed. Although these compounds are of particularvalue as photographic developers, they have other utility as in thedyeing of fur and hair.

Having thus described our invention, what we now claim and desire tosecure by U. S. Letters Patent is: v

1. A developing solution for producing a colored photographic imagecomprising as a silver halide developing agent, a i-amino-3-alkoxy-N-(,B-alkylsulfonamidoalkyl)-aniline, and a compound which couples withthe oxidation product of said developing agent at the primary aminogroup to form'a colored image on development.

2. The method of developing a silver halide emulsion which comprisestreating an exposed silver halide emulsion layer containing a latentimage, with a solution containing a compound of the following generalformula:.

l \RZNHSO2R3 Y wherein X represents a member selected from the groupconsisting of hydrogen, alkyl groups, alkoxy groups and substitutedalkoxy groups; Y represents a member selected from the group consistingof alkoxy groups and substituted alkoxy groups; R1 representsa memberselected from the group consisting of hydrogen, alkyl groups andsubstituted alkyl groups; R2 represents an alkylene radical selectedfrom the group consisting of ethylene and propylene; and R3 represents amember selected from the group consisting of alkyl groups and hydrogen,for a suilicipnt time to develop the latent image to a visible silverimage.

3. The method of developing a silver halide emulsion which comprisestreating an exposed silver halide emulsion layer containing a latentimage, with a solutioncontaining a p-phenylenediamine having an alkoxysubstituent in the ortho position with respect to the primary nitrogenatom of the p-phenylenediamine and a suli'onamidoalkyl substituentattached to the secondary nitrogen atom of the p-phenylenediamine, for asufficient time to develop the latent image to a visible silver image.

4. The method of developing a silver halide emulsion which comprisestreating an exposed silver halide emulsion layer containing a latentimage, with a solution containing a 4-amino-3- alkoxy N alkyl N (,8alkylsulfonamidoalkyl) -aniline, for a sufiicient time to develop thelatent image to a visible silver image.

5. The method of developing a silver halide emulsion which comprisestreating an exposed silver halide emulsion layer containing a latentimage, With a solution containing a 4-alkyl-N-(,B-alkylsulfonamidoalkyl)-aniline, for a sumimage, with a solutioncontaining 4-amino-3- ethoxy N ethyl N (l8 methylsulfonamido- 7 ethyl)-aniline, for a sofficient time to develop the latent image to a visiblesilver image.

8. A developing solution for producing a colcred photographic imagecomprising as a silver halide developing agent a compound of thefollowing general formula:

pound which couples with the oxidation product of said developing agentat the primary amino 7 group to form a colored image on development.

'9. A developing solution for producing a colored photographic imagecomprising as a silver halide developing agent a 4-amino-3,5 dialkoxy- Nalkyl N (5 alkylsulfonamidoalkylianiline and a compound which coupleswith the oxidation product of said developing agent at the primary aminogroup to form a colored image on development.

10. A developing solution for producing a colored photographic imagecomprising as a silver halide developing agent a 4-aminoe3-alkoxy-5-alkyl N alkyl N (B alkylsulfonamidoalkyl) -aniline and a compound whichcouples with the oxidation product of said developing agent at theprimary amino :group to form a colored image on development.

11. A developing solution for producing a colored photographic imagecomprising as a silver halide developing agent 4-amino-3-ethoxy-N- ethylN (e methylsulfonamidoethyl) -aniline and a compound which couples withthe oxidation product of said developing agent at the primary aminogroup to form a colored image on development.

ARNOLD WEISSBERGER. DUDLEY B. GLASS. PAUL W. V'IT'I'UM.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12,1940 2,304,953 Peterson Dec. 15, 1942 2,364,350 Dickey Dec. 5, 19442,374,337 Dickey Apr. 24, 1945 FOREIGN PATENTS Number Country Date804,473 France Aug. 3, 1936 536,577 Great Britain May 20, 1941 541,328Great Britain Nov. 24, 1941

2. THE METHOD OF DEVELOPING A SILVER HALIDE EMULSION WHICH COMPRISESTREATING AN EXPOSED SILVER HALIDE EMULSION LAYER CONTAINING A LATENTIMAGE, WITH A SOLUTION CONTAINING A COMPOUND OF THE FOLLOWING GENERALFORMULA: